MXPA05013355A

MXPA05013355A - Difluoride composition, method of preparation, and use for frosting glass.

Info

Publication number: MXPA05013355A
Application number: MXPA05013355A
Authority: MX
Inventors: Hugues Xavier De Roulhac
Original assignee: Seppic Sa
Priority date: 2004-12-10
Filing date: 2005-12-08
Publication date: 2006-06-14
Also published as: CA2528507A1; NO20055876L; FR2879210B1; EP1669430A1; US20060124598A1; CN1796323A; FR2879210A1; US20090039311A1

Abstract

Aqueous composition comprising at least one fluoride-ion-generating agent and at least one viscosity modifier, characterized in that its viscosity, measured at 25 DEG C. using a Brookfield(TM) LVT viscometer fitted with a No. 1 spindle rotating at a speed of 30 revolutions per minute, is between 50 and 5000 mPa.s. Method for preparing it, dry composition and method of frosting flat glass.

Description

Composition of Difluoride, Preparation Method and its Employment to Frost Glass This invention relates to novel chemical compositions, to the method for preparing them and to their use for frosting glass. The action of frosting a sheet of glass makes it translucent, without being transparent, introducing opacity by modifying its surface finish. This action results in a multitude of asperities of a few microns of depth, the macroscopic appearance of the surface, thus treated, then differs, depending on the morphology of these asperities. Therefore this results in the so-called glossy frosted glass, frosted frosted glass, opaque glass and translucent glass. Frosting is generally carried out by treating the surface with sand, when it has a large area, depositing a thin film or by chemical etching. The latter method is used more particularly in small areas or in objects of a relatively complicated configuration. The chemical etching is carried out using fluoride ions, which react with the silicon ions in the glass. The glass object is submerged, from a few seconds to a few minutes, in a bath of concentrated hydrofluoric acid or in an acid bath, containing a fluoride ion initiator, such as ammonium difluoride. The glass is then rinsed with water. Examples of known compositions for frosting glass include: that described in the German patent published under No. 1596961, which contain hydrofluoric acid and ammonium hydrogen fluoride, hereinafter referred to as ammonium difluoride, and water; that described in the British patent published under No. 1,276,550, which comprises hydrofluoric acid, a water-soluble fluoride, such as ammonium difluoride, and one or more aliphatic carboxylic acids, containing from one to three carbon atoms, which they may or may not be substituted with radicals containing one or more halogen atoms or hydroxy or amino groups, such as formic acid, acetic acid, propionic acid, monochloroacetic acid, trichloroacetic acid and glycolic acid; and the composition described in the Russian patent published under No. SU 1 675 244, which comprises hydrofluoric acid, ammonium difluoride, sodium fluorosilicate, potassium fluorosilicate and water. The applicant has also developed a novel composition based on potassium difluoride and hydrochloric acid, limiting the emission of ammonia, which has been described, together with its use, for glassware, in European patent applications EP 1 108 883 and EP 1 160 213. The combination of a difluoride containing a cation of an alkaline or alkaline-earth metal with a strong acid, improves both the effectiveness of the chemical etching as the appearance of the frosted glass obtained. When more specifically trying to flush flat glass, there are usually large area surfaces to be treated. This requires large volumes of storage of concentrated acids, which are toxic and corrosive, such as hydrochloric, sulfuric and hydrofluoric acids, and leads to the production of large quantities of undesirable effluents. It is for this reason that there is a need in the present to develop novel compositions that can be used without using the concentrated acids. The inventors have developed a novel method of frosting glass, which is pariouully suitable for frosting flat glass and does not have the aforementioned disadvantages. According to a first aspect, the object of the invention is an aqueous composition comprising at least one agent that generates fluoride ions, and at least one viscosity modifier, characterized in that the viscosity, measured at 25 ° C, using a Brookfield ™ viscometer LVT, equipped with a No. 1 axis, which rotates at a speed of 30 revolutions per minute, is between 50 and 5000 mPa-s. The term "agent that generates fluoride ions" is understood, in general, as meaning water-soluble difluoride compounds. The term "water-soluble difluoride compound" is understood, within the present patent application, as a compound or a mixture of compounds. These compounds are chosen, more particularly, from sodium difluoride (NaHF2), potassium difluoride (HF29 and ammonium difluoride (NH2HF2) or a mixture of two or all of the three salts.When the composition, as defined above, comprises a mixture of two or three difluoride compounds, among which is potassium difluoride, the latter preferably representing at least 50% by weight of said mixture.When the composition, as defined above, comprises a mixture of two or three compounds of difluoride, among which is ammonium difluoride, the latter preferably representing at most 15% by weight and more particularly at most 5% by weight of said mixture.The composition, as defined above, can also include an insoluble filler, which is more particularly chosen from: barite, gypsum, insoluble fluoride salts and, more particularly, calcium fluoride; fluorosilicates and, more particularly, calcium fluorosilicate, potassium fluorosilicate and sodium fluorosilicate; calcium phosphate, calcium sulfate, mineral oxides, in particular oxides of iron, zinc, aluminum and titanium; lignin; starch, high molecular weight ethylene oxide polymers, propylene oxide polymers and butylene oxide polymers; fatty acids and their derivatives, which are. solids at room temperature; Polymers and resins insoluble in water of high molecular weight. The invention may include one or more fillers, as defined above. The composition, as defined above, may also include a surfactant. This is selected more particularly from wetting agents and / or suspending agents, in particular from alkoxylated fatty alcohols, phosphated fatty alcohols, phosphated and alkoxylated fatty alcohols, acrylic derivatives, ethylene oxide / propylene oxide copolymers, fatty amides or cationic surfactants or fluoride derivatives of said surfactants, and silicone or fluorosilicone surfactants. The composition forming the subject of the present invention can include one or more surfactants, as defined above.

The composition, as defined above, may also include a water soluble salt. This is selected more particularly from salts containing alkali metal cations, salts containing divalent cations and salts containing trivalent cations and, more particularly, salts of calcium, magnesium, zinc, iron and aluminum. Examples are sodium chloride, manganese chloride, magnesium chloride, magnesium sulfate, calcium chloride and ferric chloride. The composition forming the subject of the present invention can include one or more water-soluble salts, as defined above. The term "viscosity modifier" is understood, within the present invention, as meaning any agent, in the proportions defined above, capable of providing the composition forming the subject of the present invention, with the appropriate rheology for the desired use for providing good flow properties, so as to spread on the glass surface. Thanks to this viscosity modifier, the composition, as defined above, has a viscosity, measured at 25 ° C, using a Brookfield ™ LVT viscometer equipped with a No. 1 shaft, which rotates at a speed of 30 revolutions per minute , between 50 and 5000 mPa-s, more particularly between 50 and 3000 mPa-s, and between 100 and 1000 mPa-s. The viscosity of the composition, as defined above, it can also be characterized by a flow time, measured with cup No. 4, according to the NFT standard 30-014, of between 10 and 60 seconds, preferably between 14 and 30 seconds. The viscosity modifier is more preferably chosen from cellulose polymers, such as, for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose or carboxymethyl cellulose, and gums and is preferably a xanthan gum or a guar gum. Examples of commercial xanthan gums are Rhodopol ™ 23 and elzan ™. An example of a commercial guar gum is Jaguar ™ HP. The composition forming the subject of the present invention can include one or more viscosity modifiers, as defined above. The object of the invention is more particularly a composition characterized in that it consists essentially, by 100% of its weight, of: 0.025% to 1.25% by weight of at least one water-soluble difluoride compound; 10% to 49.975% by weight of at least one water-insoluble difluoride compound; 0% to 39.975% by weight of at least one water-soluble salt; 0% to 5% of at least one surfactant, - 0% to 39.975% by weight of at least one to the water soluble; and 50% to 75% by weight of water; and, more particularly, a composition, as defined above, characterized in that it consists essentially, by 100% of its weight, of: 0.1% to 1% by weight of at least one speed modifier; 25% to 40% by weight of at least one water-soluble difluoride compound; 5% to 15% by weight of a water-insoluble filler; 0% to 5% of at least one surfactant; 0% to 5% by weight of at least one to the water soluble; and 50% to 75% by weight of water.

According to another aspect, the subject matter of the invention is a method for preparing a composition, as defined above, characterized in that the agent that generates fluoride ions, the viscosity modifier, in an amount sufficient to achieve the desired viscosity; and the Optional insoluble filler, surfactant and / or water-soluble salt, are mixed, with agitation, with water.

According to another aspect, the subject matter of the invention is a method for preparing a composition, as defined above, characterized in that the following is mixed, with agitation, in order to obtain 100% of its weight: -25 to 75 % by weight of a composition without water, consisting essentially of 100% by weight of: 0.05% to 5% by weight of at least one viscosity modifier; 20% to 99.95% by weight at least one water-soluble difluoride compound; - 0 to 99.95% by weight of at least one water-soluble difluoride compound; 0 to 79.95% by weight of a water-insoluble filler, and 0 to 20% by weight of at least one water-soluble filler; - with 50% to 75% by weight of water.

The water used to prepare the composition forming the object of the present invention is, generally, city supply water, whose temperature varies from about 10 ° C to 30 ° C.

The waterless composition used in the method, defined above, also constitutes a particular aspect of the present invention. The expression "without water" means that the composition does not contain added water and that any water that is present is substantially only inclusion water present in one or other of the constituent salts. In any case, the expression "without water" means a composition comprising less than 5% water by weight and preferably less than 1% water by weight. The composition without water, as defined above, is in the form of powders, granules, pellets or masses.

More particularly, it consists, per 1005 of its weight, essentially of: -0.2 to 4% by weight of at least one viscosity modifier; 50 to 80% by weight of at least one water-soluble difluroro compound; -10% to 30% by weight of a water-insoluble filler, - and 0% to 30% of at least one water-soluble salt.

The aqueous discharge composition, which forms the subject matter of the present patent application, can also be prepared by introducing each of its components in water, with agitation. Stirring is continued until a homogeneous composition is obtained and until the temperature of the preparation returns to around room temperature, ie around 12 ° C to about 25 ° C. According to a final aspect, the object of the invention is a method for frosting clean and pre-scrubbed glass, characterized in that it includes a step (a) during which the surface of the glass object is brought into contact, between 2 and 20 minutes, preferably between 2 and 10 minutes, with the solution, as defined above. This step (a) is followed, generally, by a step (b) of rinsing the frosted object, with water and then, if desired, by a step (c) of drying the object, thus rinsing. During steps (a) and (b), the frosted and rinsed compositions may be either at rest or agitated by any known mechanical means, i.e., propellants, agitators, blade agitators, brushes, circulation pumps, etc. The following examples illustrate the invention, however, without limiting it.

Example 1 (invention) (a) A mixture of dry powder was prepared in a Turbosphere ™ powder mixer from the following: This mixture took the form of a free-flowing white powder. (b) 1 kg of this mixture was emptied in 1.5 kg of water of supply of the substance, at 25 ° C, with slow agitation, at 450 revolutions per minute, by means of a propulsion stirrer. The stirring was maintained for 20 hours, so that the temperature of the bath stabilized at about 25 ° C.

A perfectly homogeneous bath, which has a viscosity of 520 mPa-s, measured using a Brookfield ™ LVT viscometer, equipped with a No. 1 shaft, which rotates at a speed of 30 revolutions per minute, and a flow time of 20 seconds.

Measured with a No. 4 cup, according to the NFT standard 30-014 was obtained. This bath was stable, without sedimentation. (c) About 1 kg of this bath was emptied into a plastic tank, in which a glass plate of 2500 cmz of area had been deposited, one of the faces of which was protected by a plastic film. After 8 minutes of immersion, the glass plate was removed from the bath and rinsed liberally with tap water at 15 ° C for 2 minutes, then allowed to air dry and the plastic film was removed. A plate treated on one side with a perfectly urm appearance and free of defects was obtained. The frost consisted of "round pyramids" on the surface of the glass, which had an average height of about 10 μp? and a width of 30 μ ?? up to 50 μt ?. The glass did not leave fingerprints when it was handled.

Example 2 (invention) (a) Drained in succession in 1.3 liters of city supply water, at 25 ° C, maintained with gentle agitation at 150 revolutions per minute, by means of a propulsion stirrer: 730 g of difluoride of ammonium, 260 g of calcium fluoride and 10 g of Kelzan standard. The stirring was maintained for 24 hours so that the temperature of the bath will stabilize at around 25 ° C. A perfectly homogeneous bath, having a viscosity of 1000 mPa-s, measured using a Bookfield ™ LVT viscometer, equipped with a No. 1 shaft, rotated at a speed of 30 revolutions per minute and a flow time of 34 seconds, measured with cup No. 4, according to BFR standard 30-014, was obtained. This bath was stable, without sedimentation. (b) About 1 kg of this bath was emptied into a plastic tank, in which a glass plate of 200 m2 of area had been deposited, one of the faces of which was protected by a plastic film. After 10 minutes of immersion, the glass plate was removed from the bath and rinsed liberally with tap water at 15 ° C for 2 minutes, then allowed to air dry, and the plastic film was removed. A frosted plate on one side, with a perfectly urm appearance and free of defects, was obtained. The frost consisted of "round pyramids", on the glass surface, which have an average height of around 9 μp? and a width of 30 μp? at 50 μta. The glass did not leave fingerprints when it was handled.

Example 3 (prior art) (a) The experiment of Example 2 was repeated with a frosting bath not containing the thickener elzan. A bath was obtained which settled quickly and, in a different way from the solutions, according to the present invention, was around 5 mPa-s, measured using a Brookfield ™ LVT viscometer, equipped with a No. 1 axis, which rotates at a speed of 30 revolutions per minute. Your flow time measured in a cup AFNOR No. 4 was 9 seconds. (b) About 1 kg of this bath was emptied into a plastic tank, in which a glass plate of 200 cm2 of area had been deposited, one side of which was protected by a plastic film. After 3 minutes of immersion, the glass plate was removed from the bath and rinsed liberally with tap water at 15 ° C for 2 minutes, then allowed to air dry, and the plastic film was removed. A frosted plate of non-urm appearance, formed of shallow "pyramids" (about 4 to 5 μp depth) was obtained, the configurations of the pyramids being less rounded than in the previous example. This surface structure left pronounced fingerprints when the glass was handled. Comparative Example 2, with Example 3, showed that the compositions, according to the invention, had an advantage in terms of frosting quality, compared to those of the prior art. This advantage was obtained by adding a strong acid to the solution.

Example 4 (invention) (a) A dry mixture was prepared in a powder mixer, of the following: This mixture took the form of a free-flowing white powder. (b) 10 kg of this mixture was emptied into 15 kg of city supply water, at 20 ° C, with rapid agitation at 1000 revolutions per minute, by means of a deflocculation sheet. The stirring was maintained for 2 hours and then the bath was allowed to stand until the temperature of the bath was stabilized at around 17 ° C. A white bath, perfectly uniform, was obtained, characterized by a flow time of 20 seconds, measured using cup No. 4, according to the NFT standard 30-014. This bath was stable, without forming sedimentation. (c) About 10 kg of this bath were emptied into a plastic tank, in which a glass plate, measuring 80 x 80 cm had been deposited, one side of which was protected by a plastic film . After 8 minutes of immersion, the glass plate was removed from the bath, its surface was scraped off by means of a rubber sheet, then liberally rinsed with hot water and finally allowed to air dry, and the plastic film was removed. . A frosted plate on one side with a perfectly uniform appearance and free of defects was obtained. The frost consisted of "pyramids" of micrometric scale, uniformly distributed over the surface of the glass. The glass did not leave fingerprints when it was handled.

Example 5 (invention) (a) A frost bath, which does not contain insoluble filler, was produced by dispersing, in succession, in 3 liters of water, 1440 g of ammonium difluoride and 20 g of guar gum. The mixture was stirred by means of a deflocculation sheet, until a homogeneous bath was obtained. The composition by weight of the obtained bath was: This bath was characterized by a flow time, measured using the AFNOR No. 4 cup, of 15 seconds. (b) A glass plate was immersed for 8 minutes in this bath and then rinsed. She had a uniform frosty appearance. The examination under a microscope showed a surface in the form of a juxtaposition of "pyramids", which has dimensions in the region of around 30 to 50 μtt ?.

Claims

CLAIMS A harassing composition, comprising at least one agent that generates fluoride ions, and at least one viscosity modifier, measured at 25 ° C, using a Brookfield ™ LVT viscometer, equipped with a No. 1 shaft, which rotates to a speed of 30 revolutions per minute, from 50 to 5000 mPa-s.
Composition, as defined in claim 1, wherein the agent that generates fluoride ions is a water-soluble difluoride compound.
Composition, as defined in claim 1, wherein the difluoride compound,, soluble in water, is selected from sodium difluoride, potassium difluoride and ammonium difluoride, or a mixture of two or all of these three salts.
Composition, as defined in any of claims 2 and 3, characterized in that, when it comprises a mixture of two or three difluoride compounds, among which is ammonium difluoride, the latter represents at least 15% by weight and preferably at most 5% by weight of said mixture.
Composition, as defined in any of claims 2 to 4, characterized in that, when it comprises a mixture of two or three difluoride compounds, among which is ammonium difluoride, the latter represents at most 15% by weight , and preferably at most 5% by weight of said mixture.
Composition, as defined in any of claims 1 to 5, characterized in that it includes at least one insoluble filler.
Composition, as defined in claim 6, characterized in that the insoluble filler is chosen from barite, gypsum, insoluble fluoride salts, and, more particularly, calcium fluoride; insoluble fluorosilicates and, more particularly, calcium fluorosilicate, potassium fluorosilicate and sodium fluorosilicate, calcium phosphate, calcium sulfate, mineral oxides, in particular iron, zinc, aluminum and titanium oxide; lignin; starch; high molecular weight ethylene oxide polymers, propylene oxide polymers and butylene oxide polymers; fatty acids and their derivatives, which are solid to the room temperature; insoluble polymers of high molecular weight, and resins or a mixture of two or more of these compounds. .
Composition, as defined in any of claims 1 to 7, characterized in that it includes at least one surfactant. .
Composition, as defined in claim 8, characterized in that the surfactant is chosen from soaking agents and / or suspending agents, more particularly from alkoxylated fatty alcohols, phosphated fatty alcohols, phosphated and alkoxylated fatty alcohols, acrylic derivatives, copolymers of ethylene oxide / propylene oxide, fatty amides, or cationic surfactants or fluoride derivatives of said surfactants, and silicone or fluorosilicone surfactants, or a mixture of two or more of these compounds. 0.
Composition, as defined in any of claims 1 to 8, characterized in that it includes at least one water soluble salt, chosen from the salts containing alkali metal cations, salts containing divalent cations and salts that they contain trivalent cations, or a mixture of two or more of these compounds and, more particularly, salts of calcium, magnesium, zinc, iron and aluminum.
Composition, as defined in claim 10, characterized in that the water-soluble salt is chosen from manganese chloride, magnesium chloride, magnesium sulfate, calcium chloride and ferric chloride, a mixture of these compounds.
Composition, as defined in one of claims 1 to 11, characterized in that, the viscosity modifier is chosen from cellulose polymers and, preferably, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy -propylmethyl cellulose or caboxymethyl cellulose, and natural gums.
Composition, as defined in claim 12, characterized in that the viscosity modifier is selected from natural gums and is preferably a xanthan gum or a guar gum.
Composition, as defined in one of claims 1 to 13, characterized in that it consists essentially, for 100% of its weight, of: 0. 02% to 1.25% by weight of at least one viscosity modifier; 10% to 49.975% by weight of at least one water-soluble difluoride compound; 0% to 39.975% by weight of a water-soluble filler, - 0% to 5% of at least one surfactant; 0% to 39.975% by weight of at least one water-soluble salt; and 50% to 75% by weight of water.
Composition, as defined in one of claims 1 to 14, characterized in that it consists essentially, per 100% of its weight, of: 0.1 to 1% by weight of at least one viscosity modifier; 25 to 40% by weight of at least one water-soluble difluoride compound; 5% to 15% by weight of a water-insoluble filler; 0% to 5% of at least one surfactant; 0% to 5% by weight of at least one water-soluble salt; and 50% to 75% by weight of water.
Method for preparing a composition, as defined in one of claims 1 to 15, characterized in that the agent that generates fluoride ions, the viscosity modifier, in an amount sufficient to achieve the desired viscosity, and the optional insoluble filler, surfactant and / or water-soluble salt are mixed with water with stirring.
Method for preparing a composition, as defined in claim 15, characterized in that the following is mixed, with stirring, in order to obtain 100% of its weight: at 50% by weight of a composition without water, consisting essentially of , for 100% of its weight, from: 0.05% to 5% in that of at least one viscosity modifier; 10% to 99.95% by weight of at least one water-soluble difluoride compound, 0% to 75.95% by weight of a water-insoluble filler, and 0% to 20% of at least one water-soluble salt; with 50% to 75% by weight of water.
Composition without water, consisting, by 100% of its weight, essentially of: 0.05% to 5% by weight of at least one viscosity modifier, 20% to 99.95% by weight of at least one water-soluble difluoride compound , 0% to 79.95% by weight of a water insoluble filler; and 0% to 20% of at least one water soluble.
Water-free composition, as defined in claim 1, consisting, by 100% of its weight, essentially of: 0.2 to 4% by weight of at least one viscosity modifier; 50% to 60% by weight of at least one water-soluble difluoride compound; 10% to 30% by weight of a water-insoluble filler; and 0% to 20% of at least one water soluble salt.
Method for frosting glass, characterized in that it includes a step (a) during which the surface of the glass object is brought into contact, for between 2 and 20 minutes, preferably between 2 and 10 minutes. minutes, with the solution defined in one of claims 1 to 15.
21. Method, as defined in claim 20, wherein step (a) is followed by a step (b) of rinsing the frosted object.